ES2770003T3 - Coatings for plastic substrates - Google Patents

Abstract

A coating composition comprising a resinous binder prepared from a reaction mixture comprising: (a) a first component; (b) a second component; and (c) a third component comprising a block copolymer having (i) a first block comprising units that have functional groups reactive with at least one of the first and second components and (ii) a second block comprising units that have functional groups that promote adhesion to a polymeric substrate, provided that the first component, the second component, and the block copolymer differ from each other, wherein the first component comprises a polyol and the second component comprises an isocyanate , and the first copolymeric block comprises units having isocyanate-reactive functional groups, and wherein the second block comprises isobornyl (meth) acrylate units.

Description

DESCRIPTION

Coatings for plastic substrates

Field of the Invention

The present invention relates to coating compositions that have adhesion to polymeric substrates. Background of the Invention

Polymers are used in a wide range of molded articles for use in the automotive, industrial, and appliance markets, among others. Vehicles, for example, include many interior and exterior parts and joints that are made of polymers, such as mirror housings, fenders, bumper covers, spoilers, dashboards, interior trim, and the like. Generally, such articles are prepared by molding an article from a polyolefin or other resin and applying one or more film-forming coating layers to the molded article to protect and / or color the article. One of the difficulties associated with the use of polymeric substrates is that it may happen that typical film-forming compositions used for protective and / or decorative coatings do not experience adhesion. In molded polymeric restoration articles, for example, the addition of an adhesion promoting layer can make the restoration process complex, tedious, and expensive. Therefore, coatings and methods are required to reduce this time and complexity.

Summary of the invention

The present invention according to claims 1 to 3 includes a coating composition comprising a resinous binder prepared from a reaction mixture comprising: (a) a first component; (b) a second component; and (c) a third component comprising a block copolymer having (i) a first block comprising units having reactive functional groups with at least one of the first and second components and (ii) a second block comprising units which they have functional groups that promote adhesion to a polymeric substrate, provided that the first component, the second component, and the block copolymer differ from each other, in which the first component comprises a polyol and the second component comprises a isocyanate, and the first copolymer block comprises units having isocyanate-reactive functional groups, and wherein the second block comprises isobornyl (meth) acrylate units. Also included in the present invention according to claims 4 to 5 is a method of treating a plastic substrate comprising (1) cleaning at least part of a plastic substrate and (2) applying the above-mentioned coating composition directly onto the clean part, in which stage (2) directly follows stage (1) with no stages in between.

The invention according to claims 6 or 7, relates to a plastic substrate comprising a deposited coating from the coating composition of any of claims 1-3, and to the use of a coating composition in any one of claims 1-3 to improve the adhesion of the applied coating layers to the plastic substrate.

Description of the Invention

For the purposes of the following detailed description, it should be understood that the invention may involve different alternative variations and step sequences, except as otherwise expressly specified. It should also be understood that the specific compositions and methods described in the following specification are merely exemplary embodiments of the invention. Furthermore, unlike any other operating examples, or where otherwise indicated, all numbers expressing, for example, amounts of ingredients used in the specification and claims are in all cases modified by the term "about" . Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations which may vary depending on the desired properties to be obtained by the present invention. At a minimum, and not in an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in light of the number of significant digits indicated and by applying standard rounding techniques.

Although the numerical ranges and parameters that establish the broad scope of the invention are approximations, the numerical values set forth in the specific examples are presented as accurately as possible. Any numerical value, however, inherently contains certain errors that are necessarily the result of the standard deviation found in their respective test measurements. Also, it should be understood that any numerical range recited herein is intended to include all subintervals subsumed in it. For example, an interval of "1 to 10" is intended to include all subintervals between (and including) the quoted minimum value of 1 and the quoted maximum value of 10, that is, it has a minimum value equal to or greater than 1 and a maximum value equal to or less than 10

The present invention generally relates to coating compositions that have adhesion to polymeric substrates. Phrases such as "having adhesion," "promoting adhesion," or "adhesion promoter," or the like, referring to a composition, refer to characteristics of this composition that reduce, if not prevent, delamination of a composition. film former from a substrate. Generally, the present coating compositions comprise a block copolymer as an adhesion promoter, wherein one of the copolymer blocks comprises units having functional groups that promote adhesion to a polymeric substrate. Methods of treating and / or coating polymeric substrates using these coating compositions are also within the scope of the present invention.

Although a block copolymer is referred to, the block copolymer can have any number of blocks and any number of monomer units. For example, the copolymer can be a diblock copolymer or a triblock copolymer. The block copolymers described herein are described with reference to blocks [A], [B], [C] and the like, each having at least 10 monomer units, where each of the blocks [A] , [B] and [C] are different from each other. For example, a diblock copolymer in accordance with the present invention may be referred to as [A] -b- [B], where the symbols [A] and [B] refer to two different blocks of the copolymer and the symbol " b "indicates the block structure of block [A] and block [B]. Similarly, the triblock copolymer according to the present invention can be referred to as [A] -b- [B] -b- [C] or [A] -b- [C] -b- [B], where Symbols [A], [B] and [C] refer to three different blocks and the symbol "b) indicates the block structure of blocks [A], [B] and [C].

A coating composition according to the present invention may comprise a resinous binder prepared from a reaction mixture comprising: (a) a first component; (b) a second component; and (c) a third component comprising a block copolymer having (i) a first block comprising units having functional groups reactive with the first and / or second components and (ii) a second block comprising units having groups functional promoting adhesion to a polymeric substrate, provided that the first component, the second component, and the block copolymer differ from each other, in which the first component comprises a polyol and the second component comprises an isocyanate, and the first copolymer block comprises units having isocyanate-reactive functional groups, and wherein the second block comprises isobornyl (meth) acrylate units. It will therefore be appreciated that the block copolymer reacts with the first and / or second component. The block copolymer can comprise up to 50 percent by weight (% by weight) of the total weight of the first, second and third components, such as up to 20% by weight, or up to 30% by weight, or up to 40 % in weigh.

At least one of the blocks of the block copolymer comprises monomeric units that promote adhesion to a polymeric substrate. The other block or blocks of the block copolymer may be selected for an appropriate reaction with the first and / or second components to produce a resinous binder and / or to provide the desired properties to the resinous binder and / or a coating composition produced from of the same.

The first component (a) and the second component (b) can be components of a coating composition that is produced from two components that react when contacted with each other, either under ambient conditions or at elevated temperature, and they comprise a polyol and an isocyanate of a polyurethane coating composition. It should be appreciated that the present invention is not limited to this specific two-component coating chemistry. Other reactive functionalities are also within the scope of the invention; for example, the first component may include a polyamine or a polyacid, and the second component may include a species reactive with the functionality of the first component, such as an epoxy, melamine, alkoxysilane anhydride, and the like.

The coating composition according to the present invention can be prepared from a reaction mixture of the first, second and third components, in which the first and second components react with each other and the first and / or second components react with the first block of the block copolymer to form a resinous binder. As such, the third component comprising the block copolymer can be prepared as a pre-polymer and thereafter the first, second and third components are then reacted together. For example, when the first component and the third component (the block copolymer) each include reactive functional groups with other functional groups on the second component, it should be understood that the second component reacts with both the first and third components. By way of a more particular non-limiting example, the first component comprises a polyol, the second component comprises a polyisocyanate, and the third component includes hydroxyl functional groups (reactive with the polyisocyanate) as well as functional groups that promote adhesion to a polymeric substrate . Upon reaction of the three components together, the resulting resinous binder (a polyurethane) exhibits improved adhesion to a polymeric substrate, compared to a resinous binder that does not include the block copolymer.

A first block (a block [A]) of the block copolymer is produced from group-reactive monomers, which is isocyanate, present in the second component. In claims 1 to 3, the first block of the block copolymer can be produced from hydroxyl-functional monomers that are reactive with groups present in the second component, such as isocyanate groups. Hydroxyl-functional monomers of the first block of the block copolymer that are reactive with isocyanate groups of the second component include hydroxyl-functional (meth) acrylic acid alkyl esters such as 2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and corresponding acrylates, or an adduct of (meth) acrylic acid / glycidyl neodecanoate. In addition, other suitable hydroxyl-containing monomers that can be used include ethylene glycol allyl ether, propylene glycol allyl ether, butylene glycol allyl ether, diethylene glycol allyl ether, hydroxymethylnorbornene, allyl alcohol, allyl alcohol. methyl, propyl alcohol and unsaturated fatty alcohols. The first block may comprise hydroxyl functional methacrylic acid alkyl esters. Alternatively, the first block of the block copolymer can be produced from amine-functional monomers that are reactive with groups present in the second component, such as isocyanate groups. Appropriate amine functional monomers of the first block of the block copolymer that are reactive with the isocyanate groups of the second component include polyamines having at least two functional groups such as di-, tri-, or higher functional polyamines, which may be aromatic and / or aliphatic.

A second block (a [B] block) of the block copolymer includes isobornyl (meth) acrylate units that have functional groups that promote adhesion to a polymeric substrate.

The block copolymer of the present invention may further include a third block, a block [C], which may be composed of monomers similar to those of block [A] or block [B] and / or include acid units (met) acrylic. For triblock copolymers having a [C] block, the blocks may be arranged according to [A] -b- [B] -b- [C] or [A] -b- [C] -b- [B] .

The block copolymer (eg, diblock or triblock) can be produced by means of controlled radical polymerization of at least one ethylenically unsaturated monomer by means of a reverse fragmentation-addition chain transfer (RAFT) mechanism, radical polymerization by Atom transfer (ATRP) or a nitroxide mediated polymerization (NMP) technique. It is understood that the first, second, and, if used, third blocks of the block copolymer can be produced in any order (sequence) and that the non-blocks may be reactive with the first and / or second component, while the Another of the blocks has functional groups that promote adhesion to a polymeric substrate.

A coating composition can also comprise the above described block copolymer of the present invention (diblock or triblock) as an additive in a coating composition. As used herein, an "additive" is a component of a composition that is not intended to function as a reactant. In this sense, a coating composition can comprise a film-forming polymer and the block copolymer of the present invention, in which the block copolymer is not intended to react with the film-forming polymer, which means that a certain reaction Lows between the block copolymer additive and the film-forming polymer may or may not occur. A block of the block copolymer additive includes the second block (the [B] block) described above having units with functional groups that promote adhesion to a polymeric substrate such as those described above. One or more blocks of the block copolymer additive can include the first block (block [A]) and / or the third block (block [C]) described above.

By "film-forming polymer" is meant a polymer that can form a continuous, self-supporting film on at least one horizontal surface of a substrate after removal of any diluents or vehicles present in the composition or after curing at room temperature or elevated temperature . The coating composition that includes the block copolymer as an additive exhibits improved adhesion to a polymeric substrate, compared to a coating composition that does not include the block copolymer additive.

The film-forming polymer can be a thermoplastic and / or thermoset polymer and can be aqueous based or solvent based.

As used herein, the term "thermoset" refers to polymer compositions that "settle" irreversibly upon curing or crosslinking, in which the polymer chains of the polymer components are joined together by covalent bonds. This property is normally associated with a crosslinking reaction of the constituents of the composition often induced, for example, by heat or radiation. Curing or crosslinking reactions can also be carried out under ambient conditions. Once cured or crosslinked, the thermosetting resin does not melt after the application of heat and is insoluble in solvents. Suitable thermosetting film-forming polymers include, for example, acrylic polymers, poly (vinyl polymers), phenolics, poly (ester polymers), poly (urethane polymers), poly (amide polymers), poly (ether polymers) , poly (siloxane polymers), their copolymers, and mixtures thereof.

As used herein, the term "thermoplastic" refers to polymeric compositions that They comprise polymeric components that are not bonded by covalent bonds and thus can undergo liquid flow upon heating and are soluble in solvents. Suitable thermoplastic film-forming polymers include, but are not limited to, acrylic polymers, thermoplastic polyolefins, such as polyethylene, polypropylene, polyamides, such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, vinyl polymers, polycarbonates, acrylonitrile-butadiene-styrene copolymers. ("ABS"), ethylene propylene and diene terpolymer rubber ("EPDM"), copolymers, and blends any of the foregoing. In general these polymers can be any such polymer made by any method known to those skilled in the art. Said polymers can be included in the solvent or be water dispersible, emulsifiable, or of limited water solubility.

The film-forming polymer can be a primer composition and / or a basecoat composition. By "primer composition" (also called "sealant") is meant a coating composition designed to adhere to substrates and function as a bonding layer between the substrate and an overlying coating composition, such as a basecoat composition. By "basecoat composition" is meant a coating composition that is normally applied to a primer composition and can include components (such as pigments and / or a flake material) that affect the color and / or visual effects of the base coating composition.

The coating composition that includes the block copolymer as an additive may further include an adhesion promoter such as a polyolefin additive, where the polyolefin additive improves the adhesion of the coating composition to a substrate. The polyolefin additive may or may not be chlorinated. Appropriate chlorinated polyolefins (CPOs) are those commercially available from Nippon Paper Chemicals under the designations SUPERCHLON E-723, E-673, and / or E-503, and appropriate non-chlorinated polyolefins are commercially available from Eastman under the tradename of ADVANTIS 510W and / or those commercially available from Nippon Paper Chemicals under the trade names of AUROREN AE 201 and / or AE-301.

The block copolymer additive and adhesion promoter additive, if used, can be provided as separate additions to the coating composition or together as a premix or as a composite material. By "composite material", it is meant that it includes a structure in which the block copolymer of the present invention encapsulates, at least partially, the adhesion promoter additive.

As used herein, the term "encapsulated" refers to a characteristic of adhesion promoter additive particles that are partially enclosed by (ie covered by) the block copolymer, to the extent sufficient to Physically separating the particles of the adhesion promoter additive from each other within a dispersion, which can be water-based or solvent-based, thus avoiding agglomeration of the adhesion promoter additive. It is appreciated that the dispersions of the composite material of the present invention may also include an adhesion promoter additive that is not encapsulated within the block copolymer. Encapsulation, or at least partial encapsulation, of the adhesion promoter additive in the block copolymer of the present invention can be achieved by adding the adhesion promoter additive in a block copolymer solution with solvent (s) where it can it happens that the adhesion promoter additive does not dissolve in it at room temperature.

The concentration of the block copolymer additive in the coating composition of the present invention can be up to 40% by weight or up to 30% by weight or up to 20% by weight. The block copolymer as described herein can be used as an additive in a concentration of at least 1% by weight, or at least 2% by weight, or at least 3% by weight, or at less than 4% by weight, or at least 5% by weight, or at least 10% by weight, or at least 20% by weight. The block copolymer as described herein can be used as an additive in a concentration of 1 to 40% by weight, or 5 to 30% by weight, based on the total solids in the coating composition .

The concentration of the adhesion promoter additive in the coating composition of the present block copolymer of the invention can be as described above as an additive in a concentration of up to 10% by weight, or up to 5% by weight, or up to 1% by weight. The adhesion promoter additive can be used as an additive in a concentration of at least 0.5% by weight, or at least 1% by weight, or at least 5% by weight. The block copolymer as described herein can be used as an additive in a concentration of 0.5 to 10% by weight, or 1 to 5% by weight, based on the total solids in the composition Coating.

The present invention is further intended for the treatment of a polymeric substrate comprising applying to at least a part of the substrate a coating composition as previously described. Particularly suitable substrates for use with the coating compositions of the present invention include plastic substrates. As used herein, the term "plastic" includes any thermoset or thermoplastic synthetic non-conductive material used in injection or reaction molding, sheet molding, or other similar processes by which parts are formed, such as, for example, acrylonitrile butadiene styrene ("ABS"), thermoplastic polyolefin ("TPO"), polycarbonate, thermoplastic elastomer, thermoset polyester, polyurethane, thermoplastic polyurethane, sheet-molded composite, and fiber-reinforced polyester glass, among others. Common examples of polyolefins are polypropylene, polyethylene, and polybutylene and include the class of thermoplastic polyolefin. Generally, TPO refers to polymer / filler mixtures that typically include a certain fraction of PP (polypropylene), PE (polyethylene), BCPP (block copolymer polypropylene), rubber, and a reinforcing filler. Common fillers include, but are not restricted to, talc, fiberglass, carbon fiber, volastonite, and MOS (metal oxy sulfate). Common rubbers include EPR (ethylene and propylene rubber), EPDM (EP-diene rubber), EO (ethylene-octene), EB (ethylbenzene), and SEB ^s (styrene-ethylene-butadienestyrene).

In treating a polymeric substrate, the coating composition of the present invention having the block copolymer as a reactant for the resin binder thereof, is suitable for use as a primer composition applied directly to a polymeric substrate and promotes adhesion to the same. When in use, the first, second, and third components are mixed together. The mixed reactants (which may include a non-reactive adhesion promoter additive, such as a polyolefin, for example, CPO) are deposited onto the polymeric substrate by any conventional method including brushing, dipping, flow coating, spraying and They allow to cure under ambient conditions or at elevated temperature, as necessary for the curing of the coating composition. The substrate can be pre-cleaned prior to deposition of the coating composition. The cleaning step refers to the removal of unwanted foreign matter from the surface, such as stains, dirt, cutting oils, waxes, finger oils and sander dust, among others. The substrate can be cleaned by, for example, mechanically separating the unwanted matter from the substrate, dissolving the unwanted foreign matter, contacting the substrate with a detergent, or a combination of two or more of these methods. As used herein, the term "detergent" refers to a substance that reduces the surface tension of water, that is, a surfactant, which is concentrated at the oil-water interface, exerts emulsifying action, and contributes to removing contaminants from the surface. Examples of detergents that could be used in the practice of the present invention include, without limitation, the anionic, nonionic and cationic surfactants described above, as well as soaps. For example, the detergent can include d-limonene, an oil extracted from citrus peel. The detergent can be provided in a cleaning composition, where the detergent can, for example, comprise from 0.01 to 10.0 percent by weight, or from 0.1 to 0.5 percent by weight. weight, or 0.1 to 0.3 weight percent of the cleaning composition, based on the total weight thereof. The amount of detergent present in the cleaning composition can vary between any combination of the mentioned values, including the indicated values.

Cleaning the substrate may include contacting the substrate with an object, such as a pad or sponge, having the cleaning composition comprising a detergent in contact with or absorbed therein. The cleaning step of the substrate may include contacting the substrate with an abrasive material having a cleaning composition comprising a detergent present therein. Abrasive materials suitable for use in the methods and systems of the present invention are commercially available and include, for example, SCOTCH-BRITE ™ Scourers, commercially available from 3M Company, St. Paul, Minnesota, and BEAR Scourers and Scourers. TEX®, commercially available from Norton Abrasives.

Contrary to conventional practice, the coating composition of the present invention having the block copolymer as a reactant for the resinous binder therein is applied directly to the clean substrate, without any other treatment of the substrate, other than optional cleaning thereof. . In this way, the conventional pretreatment steps of rubbing the substrate one or more times with a solvent and / or treating the substrate with a composition containing CPO are avoided. In accordance with the present invention, a polymeric substrate can be treated by cleaning at least a portion of the substrate and applying the composition of the present invention having a block copolymer as a reactant of the resinous binder therein, directly onto the clean part of the substrate.

The coating composition that includes the block copolymer as an additive is also suitable for use as a primer composition applied directly to a substrate (which may or may not be pre-cleaned) and to promote adhesion thereto. A polymeric substrate can be first treated by cleaning at least a portion of the polymeric substrate as described above. Directly thereafter, the clean portion is treated with an adhesion promoter, such as a polyolefin (eg, CPO), which is dried, such as by flash evaporation. The coating composition that includes the block copolymer as an additive is applied directly to the treated part of the substrate. The treatment stage and the direct application stage follow the cleaning stage without stages between the cleaning and treatment stages or between the treatment and application stages. Alternatively, the coating composition that includes the block copolymer as an additive and further comprises an adhesion promoting additive, such as a polyolefin (eg, CPO), can be applied directly to a clean polymeric substrate or an untreated polymeric substrate . By "untreated", it is meant that the substrate has not been pre-cleaned with a detergent, solvent or CPO or the like. In this way, conventional multiple CPO rubbing steps can be avoided.

In another aspect of the invention, the block copolymer can be included as an adhesion promoter. For example, the polymeric substrate can be first treated by cleaning at least a portion of the polymeric substrate as described above. Directly thereafter, the clean part is treated with an adhesion promoter comprising a block copolymer alone or in combination with a material such as a polyolefin (eg CPO), which dries. The coating composition applied thereto can either include the block copolymer as an additive (non-reactive) or as a reactive component of the coating composition.

The coating compositions of the present invention can be used as a primer composition and / or as a basecoat composition in a multilayer coating system. As such, the additional coating compositions can be applied to the coating compositions of the present invention. Examples of such additional coating compositions include decorative and / or protective coating systems, such as basecoat compositions and / or clearcoat compositions and / or colored coating compositions, as described below.

Protective and / or decorative coating systems that can be used in the present invention include, for example, protective and / or decorative coating systems that are conventionally used in automotive restoration coating applications and automotive OEM applications, among others. Examples of appropriate protective and / or decorative coating systems include single layer coating systems, such as pigmented direct gloss coating systems and multi-layer systems, such as systems including a pigmented basecoat layer and a coating layer. transparent top lining. One or more layers of the protective and / or decorative coating system may be deposited from a coating composition that includes a polymer composition that includes, without limitation, hydroxy or carboxylic acid containing acrylic copolymers, poly (ester polymers) that they contain carboxylic or hydroxyl acid and oligomers, poly (urethane polymers) containing hydroxyl or isocyanate and / or polyureas containing isocyanate or amine. The one or more layers of the protective and / or decorative coating system can be deposited from a coating composition that includes one or more other additive ingredients, including those well known in the art of surface coating formulation, such as dyes, pigments, surfactants, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts and other common auxiliary substances.

The coating compositions of the present invention can be used in the restoration of plastic articles. As used herein, the term "restoration" refers to the act of restoring or repairing the surface or finish of an item or, in the case of automobile repairs, for example, surface preparation or finishing of an uncoated replacement article together with such repair.

The following examples illustrate the invention should not be construed as limiting the invention to the detail. All parts and percentages in the examples, as well as throughout the specification, are by weight, unless otherwise indicated.

Examples

Test methods

The coatings produced in the Examples herein were tested for adhesion in a gridded adhesion test and / or a jet adhesion test.

The gridded adhesion test was carried out using a die to cut at least 11 parallel lines 2 mm apart that are placed over the layers of applied cured coating. With the retractable blade perpendicular to the panel surface, 11 parallel lines were cut through the substrate surface using a 2mm spacing die. The die was repositioned to form additional cuts at 90 degrees from the first set and cut as described above to create a 100 square grid. The film was lightly brushed with a soft or woven brush to remove any peeling flakes or coating strips. A 75 mm long (3 inch) piece of tape (3M # 898 or equivalent) was placed over the lines drawn in the same direction as a set of lines. The tape was smoothed firmly over the substrate with a rubber or back side of a blade handle. The tape was then pulled out in one continuous motion, and fast while keeping the tape as close to 60 ° as possible. The result was presented as percent adhesion of the test panel, for example, the absence of failure is recorded as 100 percent adhesion or pitch.

The jet wash test was carried out to measure the resistance of the coatings against the action of the hot water / high pressure jet scrubber. An incision was made in the paint film with a General # 88 needle to form a cross. The incisions were deep enough to cut the substrate and were approximately 10.2 cm (4 inches) in length and were at least 1/4 inch (0.64 cm) from all edges of the panel. Any plastic or paint chips caused by the cut were gently scraped or rubbed. The panel inside the jet washing chamber was adjusted and the nozzle of the jet washing machine was placed in the center of the cross, with the jet parallel to one of the branches. The jet washer was turned on and the position held. The following test conditions were used:

Pressure: 80 bar

Temperature: 60 ° C at the nozzle

Target distance: 10cm

Test trial: 60 seconds

Spray Nozzle Ventilation Jet Angle: 25 ° Nozzle 2506

Impact angle: 90 °

The result is recorded. "Pass" indicates absence of peeling of the coating on the cross. "Failure" indicates partial or total delamination.

Example 1: Synthesis of Triblock Copolymer 1

A triblock copolymer was prepared having a first block comprising acrylic acid, a second block comprising isobornyl acrylate, and a third block comprising hydroxyethyl acrylate and butyl acrylate.

Part A

The first block (Block [A]) was prepared using the materials listed in Table 1. Charge # 1 was added to a 1L four-necked glass flask equipped with a condenser, temperature measurement probe, device mechanical stirring and initiator / monomer feed inlet. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, 10% (by weight) of Charge No. 3 was introduced into the reactor and subsequently followed by Charge No. 2. The mixture of The reaction was stirred at 70 ° C for 15 minutes. After retention, the rest of Charge No. was fed. 3 for 3 hours at 70 ° C, and then the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids were experimentally measured at 32.3%, and the average molecular weight expressed in weight (Mw) was 945 g / mol and the polydispersity was 1.7 (measured by means of gel permeation chromatography using standards polystyrene).

Table 1

Part b

The second block (Block [B]) was prepared with the materials listed in Table 2. Charge # 1 was added to a 2L four-necked glass flask equipped with a condenser, temperature measurement probe, device mechanical stirring and initiator / monomer feed inlet. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, 10% (by weight) of Charge No. 3 was introduced into the reactor and subsequently followed by Charge No. 2. The mixture of The reaction was stirred at 70 ° C for 15 minutes. After retention, the rest of Charge No. was fed. 3 for 3 hours at 70 ° C, and then the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids of the resulting diblock copolymer [A] -b- [B] were measured experimentally at 51.0%, and the weight average molecular weight (Mw) was 9781 g / mol and the polydispersity was 2 , 5 (measured by gel permeation chromatography using polystyrene standards).

Table 2

continuation

Part c

The third block was prepared using the materials listed in Table 3. Charge # was added. 1 to a 2L four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and initiator / monomer power input. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, 10% (by weight) of Charge No. 3 was introduced into the reactor and subsequently followed by Charge No. 2. The mixture of The reaction was stirred at 70 ° C for 15 minutes. After retention, the rest of Charge No. 3 was fed for 4 hours at 70 ° C, and subsequently the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids of the triblock copolymer were experimentally measured at 51.0%, and the average molecular weight expressed by weight (Mw) was 11489 g / mol and the polydispersity was 4.7 (measured by permeability chromatography gel using polystyrene standards).

Table 3

Example 2: Solvent Based Primer with Triblock Copolymer 1

A thermoplastic polyolefin sheet was cleaned with a mixture of aliphatic hydrocarbon solvents and coated with a two component isocyanate based primer composition (commercially available from PPG Industries, Inc. in Europe as product D8505 / DP4000) which included as 20% by weight reactant of Triblock Copolymer 1 of Example 1. The coating was post-cured at room temperature for 24 hours and subsequently subjected to a grid adhesion test as presented in Table 4.

The results presented in Table 4 show that the coating composition of the present invention having the block copolymer as the resin binder reactant passed the grid adhesion test, while a control coating composition (without the triblock copolymer ) failure.

Table 4

Example 3: Synthesis of Triblock Copolymer 2

A triblock copolymer having a first block comprising acrylic acid, a second block comprising isobornyl acrylate, and a third block comprising butyl acrylate was prepared.

Parts A and B of Example 1 were repeated to produce a diblock copolymer. The third block was prepared with the materials listed in Table 5. Charge # 1 was added to a 3 L four-necked glass flask equipped with a condenser, temperature measurement probe, mechanical stirring device, and inlet of initiator / monomer feed. The mixture was degassed by purging with nitrogen at temperature room for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, 10% (by weight) of Charge No. 3 was introduced into the reactor and subsequently followed by Charge No. 2. The mixture of The reaction was stirred at 70 ° C for 15 minutes. After retention, the rest of Charge No. 3 was fed for 4 hours at 70 ° C, and subsequently the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids were measured experimentally at 60.9%, and the average molecular weight expressed in weight (Mw) was 15254 g / mol and the polydispersity was 5.0 (measured by means of gel permeability chromatography using standards polystyrene).

Table 5

Example 4: Aqueous Dispersion of Triblock Copolymer 2

A dispersion of the Triblock Copolymer 2 of Example 3 was prepared in deionized water with the materials listed in Table 6. Charge # 1 was added to a 1 L four-necked glass flask equipped with a condenser, measuring probe temperature, mechanical stirring device and initiator / monomer feed inlet. Charge # 2 was added to the flask slowly with stirring. After Charge # 2 was complete, Charge # 3 was fed into the flask slowly with mixing. After forming a stable dispersion, the mixture was heated to 50 ° C and the solvent generated with the block copolymer 2 was evacuated. After removing all the solvent, a stable dispersion was obtained with 31% colored solids translucent.

Table 6

Example 5: Aqueous Base Coating with Triblock 2 Copolymer Additive

The thermoplastic polyolefin ("TPO") substrates were pre-cleaned with an aliphatic hydrocarbon mixture, and then scrubbed with a chlorinated polyolefin solution and solvent evaporation allowed. The Triblock Copolymer Dispersion 2 of Example 4 was included as a 10 wt% additive in an Envirobase HP Chrysler PS2 aqueous based coating, commercially available from PPG Industries, Inc. The mixture was then applied with a 3000 WSB nozzle of SATA jet for full opacity. Following environmental dehydration, two costs of DS4000 clearcoat (commercially available from PPG Industries, Inc.) were applied. After 10 minutes of instantaneous evaporation of the solvent under ambient conditions, the final coating was heated at 60 ° C for 30 minutes.

The jet wash test and the grid adhesion test were carried out after 7 days of environmental curing as presented in Table 7. The coating composition of the present invention including the block copolymer as an additive exhibited performance superior compared to a control coating composition without the additive.

Table 7

Example 6: Synthesis of Triblock Copolymer 3

A triblock copolymer was prepared having a first block comprising acrylic acid, a second block comprising isobornyl acrylate, and a third block comprising hydroxyethyl acrylate and butyl acrylate.

Part A

The first block (Block [A]) was prepared using the materials listed in Table 8. Charge # was added. 1 to a 1L four-necked glass flask equipped with a condenser, temperature measurement probe, mechanical stirring device, and initiator / monomer power input. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. The mixture was then heated to 70 ° C, and at 70 ° C, Charge # 2 and Charge # 3 were co-fed for 3 hours. After completing the feeds, the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids were measured experimentally at 44.32%, and the average molecular weight expressed in weight (Mw) was 2339 g / mol and the polydispersity was 2.1 (measured by means of gel permeability chromatography using standards polystyrene).

Table 8

Part b

The second block (Block [B]) was prepared with the materials listed in Table 9. Charge # was added. 1 to a 3L four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and initiator / monomer power input. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, 10% (by weight) of Charge No. 3 was introduced into the reactor and subsequently followed by Charge No. 2. The mixture of The reaction was stirred at 70 ° C for 15 minutes. After retention, the rest of Charge No. was fed. 3 for 3 hours at 70 ° C, and then the reaction mixture was kept at 70 ° C until the solids were paralyzed. The final solids of the resulting diblock copolymer [A] -b- [B] were experimentally measured at 55.06%, and the weight average molecular weight (Mw) was 6989 g / mol and the polydispersity was 2 , 2 (measured by gel permeation chromatography using polystyrene standards).

Table 9

Part c

The third block (Block [C]) was prepared with the materials listed in Table 10. Charge # was added. 1 to a 3L four-necked glass flask equipped with a condenser, temperature measuring probe, mechanical stirring device, and initiator / monomer power input. The mixture was degassed by purging with nitrogen at room temperature for 15 minutes while stirring. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, Charge No. 2 and No. 3 were fed for 2 hours, and subsequently maintained at 70 ° C for 1 hour. After retention, Charge # 4 was added to the flask for 10 minutes, and thereafter the reaction mixture was kept at 70 ° C until the solids were paralyzed. Final solids were experimentally measured at 51.89%, and the average molecular weight expressed by weight (Mw) was 8261 g / mol and the polydispersity was 3.5 (measured by gel permeability chromatography using standards polystyrene).

Table 10

Example 7: Triblock 3 Copolymer with CPO Additive

A mixture of Triblock 3 Copolymer with chlorinated polyolefin was prepared with the materials listed in Table 11. Charge # 1 was added to a 1 L four-necked glass flask equipped with a condenser, temperature measurement probe, mechanical stirring device and initiator / monomer feed inlet. Subsequently, the mixture was heated to 70 ° C, and, at 70 ° C, Charge No. 2 was added to the flask. The mixture was held at 70 ° C until SUPERCHLON® 930S completely dissolved. Charge # 3 was added to the flask, and the mixture was subsequently cooled to 40 ° C, and 160 grams of solvent was removed at low pressure. The solids content of the final resin solution was 19.5%.

Table 11

Example 8: Solvent Based Primer with Triblock Copolymer 3 and CPO Additive

Thermoplastic polyolefin substrates were pre-cleaned with a mixture of aliphatic hydrocarbons. A two-component isocyanate-based primer composition, ECS25, commercially available from PPG Industries, was prepared using the material from Example 7 (20% by weight Triblock 3 Copolymer as reactant), and the primer was applied to the substrates pre-clean. The primer was cured at room temperature for 30 minutes and then coated with a basecoat, Envirobase HP Chrysler PS2, commercially available from PPG Industries, and a clearcoat, DC4010, commercially available from PPG Industries, applied as "wet overcoats". wet ", which were subsequently heated in an individual curing stage at 60 ° C for 20 minutes.

After 7 days of environmental curing, the grid adhesion test and the jet wash test were carried out as presented in Table 12. The primer with the triblock copolymer and the chlorinated polyolefin additive passed both the Grid adhesion as the jet wash test, while primer control (without triblock copolymer and chlorinated polyolefin additive) failed in both tests.

Table 12

Example 9: Aqueous Dispersion of Diblock Copolymer with CPO Additive

A dispersion was produced from the materials listed in Table 13 by placing Charge No. 1 in a 1L flask, and subsequently vacuuming ethyl methyl ketone and ethanol contributed by the Part B block copolymer of Example 1. After separating more than 90% ethyl methyl ketone and ethanol, Charge was added No. 2 to the flask and the mixture was subsequently heated to 70 ° C until complete dissolution. After dissolving completely, Charge # was added. 3 to the mixture, and then Charge No. 4. Added Load No. 5 in the mix with mix. Solvents were subjected to vacuum and a stable dispersion at 13% solids content was obtained.

Table 13

Example 10: Base Coat with Diblock Copolymer and CPO Additives

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and BYK-3560 (an adhesion promoter available from BYK USA Inc.) was subsequently rubbed onto the substrates to increase surface energy. The material from Example 9 was added in a water based coating, Envirobase HP Chrysler PS2, commercially available from PPG Industries, at 20% based on total weight, and applied to the pre-cleaned substrates to full opacity. The final coatings were heated to 60 ° C for 30 minutes after applying the clear coat, DC4010, commercially available from PPG Industries. The grid adhesion test was carried out at 20 hours and 5 days after curing as presented in Table 14. With the Block Copolymer / CPO Dispersion of Example 9 added to the basecoat, adhesion was passed in grid, while failure of the base coat occurred without the additive (control).

Table 14

Example 11: Aqueous Dispersion of Triblock Copolymer with CPO

A dispersion was produced from the materials listed in Table 15 by placing Charge No. 1 in a 1L flask, and subsequently vacuuming ethyl methyl ketone and ethanol contributed by Triblock Copolymer 1 from the Example 1. After separating more than 90% of ethyl methyl ketone and ethanol, Charge No. 2 was added to the flask and the mixture was subsequently heated to 70 ° C until complete dissolution. After dissolving completely, the Load N °. 3 to the mixture, and then Charge No. 4. Added Load No. 5 in the mix with mix. And then all the solvents were vacuum-packed and a dispersion with a 27.7% solids content was obtained.

Table 15

Example 12: Aqueous Base Coating with Triblock Copolymer 1 and CPO Additives

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and BYK-3560 was subsequently rubbed on the substrates to increase surface energy. The material from Example 11 was added in a water-based coating, Envirobase HP T472 Fine Metal Lenticular, commercially available from PPG Industries, at 20% based on total weight, and applied to the pre-cleaned substrates to full opacity. The final coatings were heated to 60 ° C for 30 minutes after applying the clear coat composition, DC4010, commercially available from PPG Industries. The grid adhesion test was carried out at 20 hours and 5 days after curing, as presented in Table 16, so that the base coat having the additive of Example 11 passes the test and the base coat without the additive (control) it caused the failure.

Table 16

Example 13: Synthesis of Triblock Copolymer 4

A triblock copolymer was prepared using the materials listed in Table 17. Charge # 1 was added to a 2L four-necked glass flask equipped with a condenser, temperature measurement probe, mechanical stirrer, and inlet monomer / initiator feed. The mixture was degassed by purging with nitrogen at room temperature for 30 minutes while stirring. The mixture was heated to 85 ° C, and at 85 ° C, Charges # 2 and # 3 were fed into the reactor for 1 hour with a 30 minute hold mid-feed. The reaction mixture was held for 1 hour after feeding, and charge # 4 was subsequently introduced into the reactor for 10 minutes and the reaction mixture was held for 1 hour. Next, charges # 5 and # 6 were introduced into the reactor for 30 minutes, and the reaction mixture was held for 1 hour before feeding # 7 and # 8 for 2.5 hours. The reaction mixture was held for 2 hours before introducing # 9 and # 10 into the reactor for 1 hour. The reaction mixture was held for 2 hours before cooling. The final solids were 57.7% by weight.

Table 17

continuation

Example 14: Aqueous Dispersion of Triblock Copolymer and non-CPO

A dispersion was produced from the materials listed in Table 18 by placing Charge No.

1 in a 1-liter flask, and subsequently vacuuming ethyl methyl ketone, DOWANOL PM and xylene contributed by Triblock Copolymer 4 of Example 13 and an unchlorinated polyolefin (Eastman 550 1 Adhesion Promoter). After removing 90% of the solvents, Charge No. 2 was added to the flask and the mixture was subsequently heated to 70 ° C until complete dissolution. After dissolving completely, Charge # 3 was added to the mixture, and then Charge # 4. Charge # 5 was added to the mixed mixture. Solvents were subjected to vacuum and a stable dispersion was obtained at 24.1% solids content.

Table 18

Example 15: Aqueous Base Coating with Triblock Copolymer 4 and Non-CPO Additives

Thermoplastic polyolefin substrates were cleaned with aliphatic hydrocarbon substrates, and BYK-3560 was subsequently rubbed on the substrates to increase surface energy. The material from Example 14 was added in a water-based coating, Envirobase HP T472 Fine Lenticular Metallic, commercially available from PPG Industries, at 20% based on total weight, and applied to the pre-cleaned substrates to full opacity. I know They heated the final coatings to 60 ° C for 30 minutes after applying the clear coat, DC4010, commercially available from PPG Industries. The grid adhesion test of the coatings and a control coating (without the copolymer / CPO additive) was performed at 20 hours and 5 days after cure as presented in Table 19.

Table 19

Example 16: Triblock Copolymer with Non-CPO Additive

Material was prepared using the components listed in Table 20. Charge # 1 was added to a 500 ml four-necked glass flask equipped with a condenser, temperature measurement probe, mechanical stirring device, and inlet of initiator / monomer feed. The mixture was heated to 80 ° C and then charge # 2 was slowly added to the flask over 30 minutes. The non-CPO dispersion was formed with triblock copolymer after mixing for 30 minutes.

Table 20

Example 17: Solvent Based Primer with Triblock Copolymer 1 and Non-CPO Additive

Thermoplastic polyolefin substrates were pre-cleaned with a mixture of aliphatic hydrocarbons. A two-component isocyanate-based primer composition, D8505 / DP4000, commercially available from PPG Industries, Inc. in Europe, was prepared using the material of Example 16 (20% by weight Triblock Copolymer 1 as reactant), and The primer was applied to the pre-cleaned substrates. The primer was cured for 30 minutes at 60 ° C.

After 7 days of environmental curing, the grid adhesion test was carried out as presented in Table 21. The triblock copolymer primer and the non-chlorinated polyolefin passed the grid adhesion test, while the control primer (without copolymer and non-chlorinated polyolefin) showed failure.

Table 21

Claims (7)

1. A coating composition comprising a resinous binder prepared from a reaction mixture comprising: (a) a first component; (b) a second component; and (c) a third component comprising a block copolymer having (i) a first block comprising units having reactive functional groups with at least one of the first and second components and (ii) a second block comprising units having functional groups that promote adhesion to a polymeric substrate, provided that the first component, the second component, and the block copolymer differ from each other, wherein the first component comprises a polyol and the second component comprises an isocyanate, and the first copolymer block comprises units having isocyanate-reactive functional groups, and wherein the second block comprises isobornyl (meth) acrylate units. 2. The coating composition of claim 1, wherein The first block comprises (meth) acrylic acid alkyl esters with hydroxyl functionality and optionally (meth) acrylic acid alkyl esters with non-hydroxyl functionality. 3. The coating composition of claim 1 or 2, wherein component (c) further comprises a third block comprising (meth) acrylic acid units and / or up to 50% by weight of the resinous binder based on the total solids. 4. A method of treating a plastic substrate comprising the steps of (1) cleaning at least a part of a plastic substrate, (2) applying the coating composition of any one of claims 1-3, directly to the part clean, where stage (2) directly follows stage (1) with no stages in between. The method of claim 4, wherein the plastic substrate comprises a thermoplastic olefin and / or further comprises applying a second coating composition directly to the coating composition of claims 1-3, wherein preferably the second coating composition comprises a base coating composition and / or a transparent coating composition. 6. A plastic substrate comprising a deposited coating from the coating composition of any of claims 1-3. 7. Use of a coating composition of any one of claims 1-3 to improve the adhesion of the applied coating layers to a plastic substrate.